US4935164A - Process for producing mouldable polymer blends - Google Patents

Process for producing mouldable polymer blends Download PDF

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US4935164A
US4935164A US06/744,273 US74427385A US4935164A US 4935164 A US4935164 A US 4935164A US 74427385 A US74427385 A US 74427385A US 4935164 A US4935164 A US 4935164A
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conductive
polymer
component
polymers
blend
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Bernhard M. Wessling
Harald K. Volk
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Zipperling Kessler GmbH and Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
    • B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
    • B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/183—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/36—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices shaking, oscillating or vibrating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/29—Feeding the extrusion material to the extruder in liquid form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/121—Charge-transfer complexes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/125—Intrinsically conductive polymers comprising aliphatic main chains, e.g. polyactylenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene

Definitions

  • conductive polymers is understood to mean polyconjugate systems, such as occur in polyacetylene (PAc), poly-1,3,5 . . . n-substituted polyacetylenes, acetylene copolymers, as well as 1,3-tetramethylene-bridged polyenes, e.g. polymers resulting from the polymerization of 1,6-heptadiene and similar polyacetylene derivatives. It also includes the various modifications of polyparaphenylenes (PPP), the different modifications of polypyrroles (PPy), the different modifications of polyphthalocyanines (PPhc) and other polymeric conductors, such as polyanilines, polyperinaphthalines etc. They can be present as such or as polymers complexed ("doped") with oxidizing or reducing substances. Complexing generally leads to an increase in the electrical conductivity by several decimal powers and into the metallic range.
  • organic conductors is understood to mean nonpolymeric, organic substances, particularly complex salts or charge transfer complexes, e.g. the different modifications of tetracyanoquinodimethane (TCNQ) salts.
  • TCNQ tetracyanoquinodimethane
  • Conductive polymers are in part obtained as polycrystalline powders, film-like agglomerates or lumps of primary particles.
  • polyacetylene is neither soluble nor fusible, it constituted an important advance when Shirakawa was able to produce self-supporting, but very thin films by interfacial polymerization, whose characteristics are similar to those of thin polymer films.
  • Tests carried out on these films concerning the morphology of polyacetylene led to a fibril theory, according to which the polyacetylene is assembled to give elongated fibres through which crystalline regions form in the fibre direction, in which the current flows along the fibre axis following doping (complexing).
  • High crystallinity e.g. polycrystalline powders, in individual cases long needle-shaped crystals (for TCNQ, cf Hanack, 1982), or other macroscopic crystal shapes, e.g. in the case of polyphthalocyanines.
  • the size of the crystallites clearly does not exceed 100 ⁇ (D. White et al, Polymer, Vol. 24, p. 805, 1983).
  • Polyconjugate polymers are, in their basic state, insulators, as opposed to polymer-bridged charge transfer complexes, such as polyphthalocyanines (cf Hanack, loc. cit, pp. 269/270).
  • Optical appearance generally matt black (glossy or shining only if the synthesis was carried out on the smooth surfaces, cf the Shirakawa method for producing self-supporting "films", in which the side facing the glass is glossy and that remote from the glass matt).
  • Polyphthalocyanines are non-glossy powders, which appear blue.
  • Conductive polymers and organic conductors are generally insoluble, infusible and not shapable, whilst in most cases being unstable relative to oxygen, moisture and elevated temperatures. If e.g. in the case of nonpolymeric or polymeric charge transfer complexes (TCNQ or PPhc), melting points can in fact be observed, they are close to the decomposition point, so that decomposition-free melting is either impossible or is only possible with great difficulty. To the extent that soluble derivatives exist in the case of the different conductive polymers, their conductivity is several decimal powers inferior compared with the insoluble non-modified substances. A thermoplastic deformation of conductive polymers and organic conductors has not as yet proved possible.
  • Polypyrrole and certain representatives of the polyphthalocyanines are comparatively stable with respect to oxidative and thermal influences, cf Hanack, loc. cit; K. Kanazawa et al, J. Chem. Soc., Chem. Comm. 1979, pp. 854/855.
  • Solvents have also not hitherto been described for other conductive polymers. Attempts have been made for polyphthalocyanines to increase the solubility by introducing ring substituents, e.g. tert.butyl groups, but the conductivity decreases by several decimal powers. T. Inabe et al, J. Chem. Soc., Chem. Comm, 1983, pp. 1984-85 describe the dissolving of polyphthalocyanine in trifluoromethane sulphonic acid, but give no information on the characteristics of the raw material recovered therefrom.
  • EP-OS 62,211 describes polyacetylene suspensions these are in fact only suspended, coarse polyacetylene particles, without deagglomeration of the tertiary or secondary structure of the particles.
  • meltable or fusible conductive polymers have occasionally been described, but their conductivity was never satisfactory and was several decimal powers lower than in the case of the polymers under discussion here.
  • Cis-polyacetylene to a certain extent would appear to represent an exception in that immediately following production is to a limited extent "ductile", as described by M. Druy et al, J. Polym. Sci., Polym. Phys., Vol. 18, pp. 429-441, 1980. However, the ductility and stretchability is limited exclusively to the cis-isomer, the transisomer being brittle even in the absence of oxygen. A. MacDiarmid and A.
  • J. Hocker et al (EP-OS 62,211) describe the production of moulded articles from polyacetylene-containing polymers, which are dissolved in a solvent containing macroscopic polyacetylene particles. Shaping takes place by removing the solvent. For accelerating suspension formation, optionally an Ultraturrax® stirrer is used, the fibrous structure of the particles being retained. The thus obtained moulded articles have only a comparatively low conductivity.
  • the further EP-OS 84,330 of the same inventors also deals with attempts to obtain moulded articles from polyacetylene-containing plastics, without using a master forming process.
  • DE-OS 3,227,914 describes a process, in which polypyrrole is moulded at temperatures of 150° to 300° C. and pressures of 50 to 150 bar. According to the examples, this process is suitable for producing multilayer laminates of nonconductive polymer films and polypyrrole films (as are directly obtained from electrochemical polymerization).
  • polypyrrole and the various copolymers thereof are pressed in film form onto polyester, polyethylene or polyacrylonitrile films or on polyurethane or polystyrene foam.
  • thermoplastic flowability of the non-conductive polymer films permits the use thereof as binders.
  • TCNQ salts in the form of a crown ether complex are incorporated into a thermoplastic polymer matrix. Whilst the finished compound can be readily shaped and has good mechanical characteristics, the conductivity of max. 10 -6 Siemens/cm is far from adequate and is several decimal powers below the value of the TCNQ salts.
  • conductive polymers and organic conductors together have a number of restricting disadvantages (insolubility, poor dispersibility, inadequate softening ranges or glass transition temperatures, non-existent melting points and lack of stability relative to oxygen, heat and in part crosslinking processes), which have hitherto prevented the industrial utilization thereof.
  • these disadvantages like the conductivity, are particularly due to the relatively high degree of crystallinity of the conductive polymers and organic conductors, as well as the in part considerable reactivity, particularly with respect to oxygen.
  • the invention relates to a process for producing mouldable polymer blends from electrically conductive organic polymers and/or organic conductors, as well as a matrix polymer, which is characterized in that substantially monomer-free, electrically conductive organic polymers and/or organic conductors are dissolved or dispersed in a melt or solution of a thermoplastic polymer or polymer mixture partially compatible therewith and having a solubility parameter of >8.6 (cal/cm 3 ) 1/2 until a homogeneous material has formed which, when visually observed, has a different colour from the conductive organic polymers and/or organic conductors and matrix polymers used, and optionally the solvent is then removed.
  • Blends are considered to be homogeneous which, apart from a few rare coarser particles to be looked upon as faults, have an average particle size below 20 microns, preferably below 5 microns and in optimum cases around and below 1 microns e.g. 50 to 200 nm (electron-microscopically detectable).
  • Suitable matrix polymers are thermoplastic polymers with high solubility parameter and a surface tension of >35 dyn/cm such as polyethers, polyesters, polyvinylidene chloride or fluoride, polyamide, polycaprolactone, polyurethane, cellulose partially esterified with acetic, propionic or butyric acid, partially esterified polyvinyl alcohol or partially esterified polyvinyl acetate, polyvinyl pyrrolidone, polyvinyl butyral, water-soluble or water-swellable polymers such as e.g. polyacrylic acid, liquid-crystalline polymers such as e.g.
  • thermoplastic liquid-crystalline polyesters ionomers or polymers having polar functional groups, polyacrylonitrile, copolymers thereof or mixtures of the aforementioned polymers. It is also possible to use reactive monomer and/or prepolymer mixtures, which can be completely polymerized to the matrix polymer after producing the dispersion. Examples are caprolactam, diol/dicarboxylic acid and diisocyanate/diol/polyester or polyether mixtures or other suitable reaction (injection) moulding materials.
  • the secondary and tertiary structures (agglomerates) obtained during the polymerization of the conductive polymers are extensively disintegrated, i.e. preferably down to the primary particles.
  • the electrically conductive polymer blends that the conductive particles are in contact and that for this purpose the concentration of the conductive polymer or organic conductor is above the volume concentration critical for the electrical conductivity, i.e. the so-called percolation point.
  • a description of the physical laws of percolation in connection with the example of electrically conductive carbon black is given by K. Miyasaka J. Mat. Sci., Vol. 17, pp. 1610 to 1616, 1982.
  • the concentration is preferably in the vicinity of the interfacial--energy equilibrium, where the sum of the cohesion energy is equal to the sum of the adhesion energy and occurs through chain formation.
  • the quantity of conductive polymers and/or organic conductors in the polymer blend can be between 3 and 35% by weight, as a function of the chosen material pairs and preferably the concentration is at least 8% by weight.
  • the concentration may be still lower, i.e. between about 0.5 and 3% by weight, if it is desired to prepare antistatic mixtures.
  • the dispersion of the conductive polymer and/or organic conductor in the physical--chemical partially compatible matrix polymer according to the invention is largely achieved through the high interfacial energy between the participating substances.
  • matrix polymers with a particularly high surface tension are used.
  • the matrix polymer is either melted accompanied by heating and shearing or is dissolved in a suitable solvent, which is then removed.
  • Polymers with low solubility parameters such as polyolefins or olefin copolymers with a solubility parameter of ⁇ 8.6 (cal/cm 3 ) 1/2 are less suitable according to the invention.
  • agglomeration occurs, so that polycrystalline microcrystal needles or fibrils of approximately 5 to 50 microns form, which through contact with one another can lead to a conductivity of the polymer blend.
  • amorphous powders of the conductive polymers if, in place of matrix polymers with high solubility parameters, those with low solubility parameters well below 8.6 (cal/cm 3 ) 1/2 are used, e.g. polyethylene, and ultrasonics are applied to the melt, so that the aforementioned microcrystal needles or fibrils form.
  • the organic conductor e.g. a TCNQ charge transfer complex
  • a suitable matrix polymer e.g. polycaprolactone
  • solvents or applying a melt optionally assisting the dissolution by ultrasonics and/or heat; by slowly cooling or tempering the conductor crystallizes in the form of thin needles in the melt or the solidifying polymer, said needles preferably contacting each other.
  • Antistatic or electrically conductive moulded articles are obtained in this manner.
  • Chain-like strings or spherical primary particles form in the continuous polymer matrix and above the percolation point. This leads to a type of interfacial-energy equilibrium through the formation of the same number of contact points between the conductive polymer particles, as between the latter and the matrix polymer.
  • the conductive particles form submicroscopic, widely branched conductor paths or a through conductor network.
  • the electrical conductivity of the organic polymers can be significantly increased by doping (complexing) before or after the production of the polymer blend.
  • Complexing agents which are suitable are known per se, iodine, antimony or arsenic pentafluoride, tetrafluoro boric acid, perchlorates, sulphurtrioxide, sulphonates or metal salts and in particular iron(III)-chloride being particularly suitable for p-doping and butyl lithium, triphenylhexyl-lithium, naphthalin-sodium and the like being particularly suitable for n-doping.
  • each p-doped particle, isolated by the matrix polymer is surrounded by n-doped particles and vice versa.
  • external energy sources e.g. laser light
  • the particles can be excited in a clearly defined manner to give conductive, three-dimensional structures.
  • a homogeneous doping can be obtained, if doping (complexing) is performed with the doping agent (e.g. I 2 or FeCl 3 ) in a solution and under ultrasonic action.
  • the doping agent e.g. I 2 or FeCl 3
  • the completely polymerized and undoped conductive polymers e.g. PAc or PPhc
  • the monomers e.g. pyrrole
  • the product is recovered by filtration, centrifugation and/or lyophilization.
  • the doping of e.g. polyacetylene under the action of ultrasonics in a solution or dispersion leads to completely different characteristics (particularly more uniform doping, higher conductivity and crystallinity or greater extension of the crystallites, increased stability, improved processability) of the conductive polymers compared with doping of e.g. foils or films through gaseous complexing agents (J 2 , AsF 5 , etc) or suspended, macroscopically large particles (cf e.g. EP-OS 62,221) through dissolved complexing agents (e.g. FeCl 3 ). If the latter process is called a "heterogeneous" doping process, then the presently found process can be called a "homogeneous" doping process.
  • gaseous complexing agents J 2 , AsF 5 , etc
  • macroscopically large particles cf e.g. EP-OS 62,221
  • FeCl 3 dissolved complexing agents
  • Homogeneously doped PAc in polymer blends e.g. with cellulose propionate forms microscopically fine homogeneous, possibly liquid-crystalline particles or fibres of below 20 microns, which under the microscope through a polarization filter dark position appear bright and are highly conductive.
  • antioxidants e.g. phenolic antioxidants
  • crosslinking inhibitors e.g. phosphonites
  • light-collecting, fluorescent dyes are added for producing photoconducting polymer blends.
  • the polymer blends produced according to the invention have the particular advantage that the conductive polymer is very well protected against oxidative decomposition and/or crosslinking both during dispersion and during the subsequent shaping process, as a result of the dispersion in the matrix polymer. This can be in particular optimized by the choice of matrix polymers with particularly low O 2 and H 2 O permeability coefficients.
  • the polymer blends according to the invention and the moulded articles produced therefrom have a different colour compared with the pulverulent starting substances or simple mechanical mixtures thereof.
  • the colour is characteristic of the particular conductive polymer and can be measured on ultra-thin coatings.
  • the polyacetylene colour e.g. changes from black to deep blue, a sign of the conductive polymer being truly dispersed in the polymer matrix.
  • Polychromism occurs in the case of poly- ⁇ -cyano(phthalocyaninato)cobalt (III).
  • Ultrasonics are preferably used for dispersion purposes when the compatibility of the carrier polymer with the conductive polymer to be dispersed or the interfacial energy is not sufficient for wetting the primary particles in this way alone and consequently break down the secondary and tertiary structures.
  • the conductive polymer should be free of monomer and preferably also free of oligomer.
  • the invention also relates to an apparatus for performing the process according to the invention using ultrasonics. It is an extruder characterized in that one or more sonotrodes project into the transformation zone through the barrel wall.
  • the apparatus is illustrated by the attached drawings, wherein show:
  • FIG. 1 a longitudinal section through a screw extruder according to the invention.
  • FIG. 2 a section through a disk extruder according to the invention at right angles to the driving shaft.
  • FIG. 3 a section through a kneader (internal mixer) with a die.
  • a sonotrode is immersed in free-swinging manner in the mass for carrying out the inventive process of ultrasonics-supported dispersion of the conductive organic polymer and/or organic conductor in a melt or solution of the matrix polymer.
  • a power supply, a converter, a booster (transducer) and the actual sonotrode are required for ultrasonics generation. These parts are matched to one another in such a way that the maximum oscillation energy is roughly 20 kHz per sonotrode at the sonotrode end face.
  • the sonotrode can be made from aluminium or preferably titanium steel.
  • the total power provided by the sonotrode or sonotrodes should be 5 to 30% of the drive power of the extruder motor.
  • the 135 mm long sonotrode 17 projects through the barrel wall 11 into the transformation zone 16 of a screw extruder.
  • the screw flights 14 are partly ground away, so that reduced height flights 15 are obtained, whilst a space is formed into which the sonotrode can project.
  • the end face 18 of sonotrode 17 is arranged at right angles to the sonotrode axis.
  • the sonotrode is connected to the extruder, a barrier on the sonotrode at the zero passage of the oscillations (e.g. with half the length) prevents a possible advance of the melt to the booster.
  • the starting materials are supplied under a protective gas atmosphere to the extruder by means of the charging hopper 13.
  • the extruder is either filled with inert gas or is operated in vacuo in order to prevent oxidative decomposition of the conductive organic polymers and/or organic conductors.
  • the apparatus according to the invention can also be a modified disk extruder.
  • Such disk extruders are fundamentally known, cf Z. Tadmor et al, Plastics Engineering, Part I, pp. 20-25, 1979 and part II, 11-34-39, 1979.
  • Such a disk extruder comprises a cylindrical casing 21 and a driven shaft 22, on which are arranged a plurality of parallel disks 24. Normally, mixing fingers project into the gaps between the disks and improve the thorough mixing of the components by shearing.
  • one or more of these mixing fingers are replaced by sonotrodes 27. It is advantageous in this case, if the end faces 28 of the sonotrodes 27 are at an angle to the sonotrode axis. Angles between 30° and 60°, preferably an angle of approximately 45° are suitable.
  • charging takes place by means of the supply hopper 23 under a protective gas atmosphere, whilst the actual apparatus can either be operated under a protective gas atmosphere or in vacuo, in order to exclude moisture and oxygen.
  • FIG. 3 shows another embodiment of the apparatus in the form of a pressure arm-operated kneader or internal mixer.
  • the kneading blades 32 rotate in opposite directions about their shafts 33.
  • Sonotrode 37 projects from above into the kneading chamber so that the sound pressure waves emanating from the end face 38 act on the material being kneaded.
  • the invention finally relates to the use of the polymer blends obtained with the aid of the inventive process for producing moulded articles, particularly for electrical components such as conductors, semiconductors or photoconductors.
  • electrical components such as conductors, semiconductors or photoconductors.
  • the polymer blends it is possible e.g. to produce electrical components such as semiconductor relays, thyristors or the like, as well as batteries.
  • Photovoltaic uses e.g. in solar technology for directly producing electric power from light are also possible.
  • Other uses are permanent antistatic packagings or components for information storage and processing.
  • All the conductive polymers form under conventional conditions of hetergeneous polymerization, sphere-like primary particles, which aggregate in an unordered manner.
  • the conductivity mechanisms are the same in pure, unshaped crude conductive polymers comprising aggregated primary particles alone as in the homogeneous polymer blend above the percolation point.
  • An optimum case for a conductive polymer blend is consequently a homogeneously doped conductive polymer, which is homgeneously dispersed in ultra-finely divided form in the matrix polymer, the latter also exercising a protective function against possible oxygen attack.
  • the TCNQ-N-methylquinoline complex may be incorporated in polycaprolactone in the form of needles in an analogous manner.
  • a dissolution of the needles could be achieved (a) by applying ultrasonics and/or (b) by heating the mass to 120° to 190° C. for 0.5 to 2 minutes.
  • crystallization in the form of fine needles can be achieved resulting in similar conductivities as in Table 1.
  • the product obtained (approx. 50 g) was dispersed under ultrasonic action in 1n NaOH (1010 ml) and was exposed to sound waves for approximately 1 hour, after which the product was filtered and rinsed three times with water.
  • the PPy lost approximately 50% of its weight. After drying, the PPy had a conductivity of 10 -3 Siemens/cm.
  • the basic-treated PPy was then again dispersed with ultrasonics, but in 1 liter of a mixture of 1 part 35% hydrochloric acid and 3 parts methanol. After filtering and washing three times with methanol, the product was dried and was found to have a conductivity of 10 Siemens/cm.
  • the homogeneously doped PAc was incorporated in polycaprolactone (surface resistance 10 12 ⁇ ) in a dispersion kneader applying ultrasonics. Using 49.5 grams of polycaprolactone and 0.5 grams of PAc the following results were obtained (at a mass temperature of 60° C.): 15 minutes dispersion time: bluish, semi-transparent film with some dots, 10 10 ⁇ , 60 minutes dispersion time: intense blue, semi-transparent film, almost free of dots, 10 9 ⁇ .
  • polyacetylene was incorporated into a polyethylene melt.
  • the mass obtained contained visually detectable black particles (spots) following extrusion.
  • a film produced from the polymer bath had no blue colouring.
  • polyethylene is normally an unsuitable matrix polymer for the purposes of the inventive process.
  • FIGS. 4 and 5 show the transition spectra of the polymer blend produced according to the invention, namely FIG. 3 for polypyrrole in cellulose propionate, FIG. 5 curve A 0.5% polyacetylene in cellulose propionate, curve B 0.44% poly- ⁇ -cyano(phthalocyaninato)cobalt (III) in cellulose propionate.

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JPS6116931A (ja) 1986-01-24
EP0168620A3 (en) 1986-06-11
JPH0668029B2 (ja) 1994-08-31
ATE67893T1 (de) 1991-10-15
CA1296500C (en) 1992-03-03
EP0168620B1 (de) 1991-09-25
KR860000328A (ko) 1986-01-28
DE3422316A1 (de) 1985-12-19
KR930001984B1 (ko) 1993-03-20
DE3584192D1 (de) 1991-10-31
EP0168620A2 (de) 1986-01-22
DE3422316C2 (de) 1986-11-20

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